Estimated daily intake and cumulative risk assessment of organophosphate esters and associations with DNA damage among e-waste workers in Hong Kong.

Organophosphate esters (OPEs) are extensively used as additives in various products, including electronic equipment, which becomes e-waste when obsolete. Nevertheless, no study has evaluated OPEs exposure levels and the related health risks among e-waste workers in Hong Kong. Therefore, 201 first-spot morning urine samples were collected from 101 e-waste workers and 100 office workers to compare eight urinary OPE metabolites (mOPEs) levels in these groups. The concentrations of six mOPEs were similar in e-waste workers and office workers, except for significantly higher levels of diphenyl phosphate (DPHP) in e-waste workers and bis(1-chloro-2propyl) phosphate (BCIPP) in office workers. Spearman correlation analysis showed that most non-chlorinated mOPEs were correlated with each other in e-waste workers (i.e., nine out of ten pairs, including di-p-cresyl phosphate (DpCP) and di-o-cresyl phosphate (DoCP), DpCP and bis(2-butoxyethyl) phosphate (BBOEP), DpCP and DPHP, DpCP and dibutyl phosphate (DBP), DoCP and BBOEP, DoCP and DPHP, DoCP and DBP, BBOEP and DPHP, DPHP and DBP), indicating that handling e-waste could be the exposure source of specific OPEs. The median values of estimated daily intake (EDI) and hazard quotient (HQ) suggested that the health risks from OPEs exposures were under the recommended thresholds. However, linear regression models, Quantile g-computation, and Bayesian kernel machine regression found that urinary mOPEs elevated 8-hydroxy-2-deoxyguanosine (8-OhdG) levels individually or as a mixture, in which DPHP contributed prominently. In conclusion, although e-waste might not elevate the internal OPEs levels among the participating Hong Kong e-waste workers, attention should be paid to the potential DNA damage stimulated by OPEs under the currently recommended thresholds.

Investigation of Urinary Metabolites of Organophosphate Esters in Hanoi, Vietnam: Assessment Exposure and Estimated Daily Intake.

In recent years, organophosphate esters (OPEs) have become one of the most common additives in various consumer products worldwide, therefore the exposure and impact of OPEs on human health are drawing a lot of attention. In this study, three metabolites of OPEs including bis(1,3-dichloro-2-propyl) phosphate (BDCIPP), diphenyl phosphate (DPhP) and diethyl phosphate (DEP) were investigated in first-morning void urine samples taken from a population (age range: 3-76 years old) in Hanoi, Vietnam. The most dominant urinary OPE metabolite was DEP with the geometric mean of specific gravity adjust (SG-adjusted) concentration were 1960 ng mL-1 and detected frequency (DF) of 98%. Followed by DPhP (8.01 ng mL-1, DF: 100%) and BDCIPP (2.18 ng mL-1, DF: 51%). The results indicated that gender and age might have associations with the OPE metabolites variation in urine samples. The levels of OPE metabolites in urine samples from females were slightly higher than in males. An increase in age seems to have an association with a decrease in DPhP levels in urine. Exposure doses of parent OPEs were evaluated from the unadjusted urinary concentration of corresponding OPE metabolite. The estimated exposure doses of triethyl phosphate (TEP) (mean: 534,000 ng kg-1 d-1) were significantly higher than its corresponding reference dose, suggesting the high potential risk from the current exposure doses of TEP to human health. The results of this work provided the initial information on the occurrence of three OPE metabolites in urine from Hanoi, Vietnam and estimated exposure dose of corresponding parent OPEs.

A state-of-the-science review of analytical methods for urinary dialkylphosphate metabolites in the assessment of exposure to organophosphate pesticides: From 2000 to 2022.

The general population and workers are exposed to organophosphate insecticides, one of the leading chemical classes of pesticides used in rural and urban areas. This paper aims to conduct an integrative review of the most used analytical methods for identifying and quantifying dialkylphosphate-which are metabolites of organophosphate insecticides-in the urine of exposed workers, discussing their advantages, limitations and applicability. Searches utilized the PubMed, the Scientific Electronic Library Online and the Brazilian Digital Library of Theses and Dissertations databases between 2000 and 2021. Twenty-five studies were selected. The extraction methods most used were liquid-liquid extraction (LLE) (36%) and solid-phase extraction (SPE) (36%), with the SPE being more economical in terms of time and amount of solvents needed, and presenting the best percentage of recovery of analytes, when compared with LLE. Nineteen studies (76%) used the gas chromatography method of separation, and among these, 12 records (63%) indicated mass spectrometry used as a detection technology (analyzer). Studies demonstrate that dialkylphosphates are sensitive and representative exposure biomarkers for environmental and occupational organophosphate exposure.

Residual Dialkyl Phosphate Metabolite Concentrations of Organophosphate Pesticides Among Indian Farmworkers: Implication of Exposure and Hazard Assessment.

OBJECTIVE: Biomonitoring of urinary dialkyl phosphate (DAP) metabolites, a sensitive biomarker to assess pesticides exposure and also to study the impact of the use of personal protective equipment (PPE). METHODS: A preintervention-postintervention study to biomonitor dimethylphosphate, diethylphosphate, diethylthiophosphate, and diethyl-dithiophosphate using liquid chromatography with tandem mass spectrometry among Indian farmworkers (n = 120). RESULTS: Dimethylphosphate was detected in all samples at a mean concentration of 74.91 µg · L -1 (17.616 µg · g -1 creatinine), whereas diethylthiophosphate and diethyl-dithiophosphate were detected in 88% and 82% of samples, respectively, among farmworkers who adopted unsafe pesticide-handling practices. Intervention studies showed a significant reduction in the urinary DAP metabolites detected among the farmworkers using PPE provided to them ( P < 0.01). CONCLUSIONS: Study confirms the exposure to pesticides among farmworkers and highlights the importance of the use of PPE to minimize exposure.

Factors affecting urinary organophosphate pesticide metabolite levels among Californian agricultural community members.

Organophosphate (OP) pesticides are widely used in California for agricultural pest and weed control despite their well-documented adverse health effects among infants, children, and adults. We sought to identify factors affecting urinary OP metabolites among families living in high-exposure communities. Our study included 80 children and adults who lived within 61 m (200 ft) of agricultural fields in the Central Valley of California in January and June 2019, which are pesticide non-spraying and spraying seasons, respectively. We collected one urine sample per participant during each visit to measure dialkyl phosphate (DAP) metabolites; these were coupled with in-person surveys to identify health, household, sociodemographic, pesticide exposure, and occupational risk factors. We used a data-driven, best subsets regression approach to identify key factors that influenced urinary DAPs. Participants were mostly Hispanic/Latino(a) (97.5 %), over half were female (57.5 %), and most households reported having a member who worked in agriculture (70.6 %). Among the 149 urine samples suitable for analysis, DAP metabolites were detected in 48.0 % and 40.5 % of samples during January and June, respectively. Total diethyl alkylphosphates (EDE) were only detected in 4.7 % (n = 7) of samples, but total dimethyl alkylphosphates (EDM) were detected in 41.6 % (n = 62) of samples. No differences were observed in urinary DAP levels by visit month or by occupational exposure to pesticides. Best subsets regression identified several individual- and household-level variables that influenced both urinary EDM and total DAPs: the number of years spent living at the current address, household use of chemical products to control mice/rodents, and seasonal employment status. Among adults only, we identified educational attainment (for total DAPs) and age category (for EDM) as significant factors. Our study found consistent urinary DAP metabolites among participants, regardless of spraying season, and identified potential mitigating factors that members of vulnerable populations can implement to protect their health against OP exposure.

Exposure assessment of aryl-organophosphate esters based on specific urinary biomarkers and their associations with reproductive hormone homeostasis disruption in women of childbearing age.

The effects of aryl-organophosphate esters (aryl-OPEs) on female reproduction health are still unclear owing to the lack of specific exposure biomarkers. Here, we analyzed the hydroxylated metabolites of three aryl-OPEs (phenyl diphenyl phosphate [TPhP], 2-ethylhexyl diphenyl phosphate [EHDPP], and tricresyl phosphate [TCrP]) and diphenyl phosphate (DPhP) in urine samples from 913 women of childbearing age, and explored the association between exposure to the aryl-OPEs and reproductive hormone levels. The detection frequencies of 2-ethyl-5-hydroxyhexyl diphenyl phosphate (5-OH-EHDPP), phenyl di-p-tolyl phosphate (4-OH-MDTP), and 4-hydroxyphenyl diphenyl phosphate (4-OH-TPhP) were 94.6 %, 93.3 %, and 84.2 %, respectively. Multivariate linear regression analyses revealed that the quartiles of 4-OH-TPhP were positively associated with the progesterone (P4) level (p-trend = 0.008), and the P level in the highest quartile of 5-OH-EHDPP was 7.2 % (95 % CI, 5.7 % to 8.7 %) higher than that in the lowest quartile. The 17ß-estradiol levels in the highest quartiles of 4-OH-TPhP and 5-OH-EHDPP were 15.0 % (95 % CI, 13.7 % to16.1 %) and 5.9 % (95 % CI, 15.7 % to 16.1 %) lower than those in the lowest quartiles, respectively. The anti-Müllerian hormone level linearly increased across the quartiles of 4-OH-MDTP (p-trend = 0.036), and the follicle-stimulating hormone exhibited the opposite trend (p-trend = 0.0047). These results indicate that aryl-OPEs may disrupt hormone homeostasis using their specific biomarkers and may negatively affect female reproduction.

Rapid and sensitive analytical procedure for biomonitoring of organophosphate pesticide metabolites in human urine samples using a vortex-assisted salt-induced liquid-liquid microextraction technique coupled with ultra-high-performance liquid chromatography/tandem mass spectrometry.

RATIONALE: Organophosphate pesticides (OPPs) are the most commonly used insecticides around the world in various agricultural and domestic practices, and humans are frequently exposed to these hazardous insecticides that can lead to several chronic health effects. Therefore, a fast and sensitive analytical method is required for biomonitoring the markers of OPPs in humans for exposure estimation. In this study, a fast and sensitive analytical procedure was developed for the determination of the metabolites of OPPs in human urine samples. METHODS: Metabolites of OPPs were extracted from 2 mL of urine sample using a novel vortex-assisted salt-induced liquid-liquid microextraction (VA-SI-LLME) technique, and the preconcentrated metabolites were analyzed by ultra-high-performance liquid chromatography/tandem mass spectrometry (UHPLC/MS/MS). Various factors affecting the efficiency of VA-SI-LLME were thoroughly investigated. RESULTS: The metabolites of OPPs exhibited very good linearity over the concentration range between 0.05 and 50 ng mL-1 with coefficient (r2 ) values ranging between 0.9986 and 0.9999. The method showed excellent sensitivity with detection limits ranging from 0.01 to 0.03 ng mL-1 and quantification limits from 0.03 to 0.05 ng mL-1 . The developed method was applied to the analysis of real samples and the recoveries ranged between 85.0 and 114.1% with related standard deviations <5%. CONCLUSIONS: The results showed the VA-SI-LLME/UHPLC/MS/MS method to be a simple, rapid, sensitive, and selective analytical procedure for the biomonitoring of the metabolites of OPPs in humans. This efficient and cost-effective analytical method could be a potential alternative method for the biomonitoring of the metabolites of pesticides in humans.

Urinary biomarkers for assessment of human exposure to monomeric aryl phosphate flame retardants.

While monomeric aryl organophosphate flame retardants (m-aryl-OPFRs) are used worldwide in a variety of consumer products, specific biomarkers for epidemiologic studies are lacking. To explore the potential of urinary hydroxylated metabolites of m-aryl-OPFRs as the biomarkers, we detected triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPP), and tricresyl phosphate (TCrP) in 259 whole blood samples and their 5 hydroxylated and 2 diester metabolites in the paired urine samples from the general population. 2-Ethyl-5-hydroxyhexyl diphenyl phosphate (5-OH-EHDPP), 4-hydroxyphenyl diphenyl phosphate (4-OH-TPHP), and 3-hydroxy-4-methylphenyl di-p-tolyl phosphate (3-OH-MDTP) were detected in >80% of urine samples after enzymatic hydrolysis of conjugates, and their concentrations showed significant positive correlations with the blood concentrations of their corresponding parent compounds, respectively. To characterize the temporal reliability, the m-aryl-OPFRs metabolites were also determined in urine samples repeated nine times from six volunteers over 3 months. Urinary 5-OH-EHDPP showed strong temporal reliability (creatinine-corrected intraclass correlation coefficients (ICCs), 0.77; 95% confidence interval [CI], 0.58 to 0.90), and urinary 3-OH-MDTP (creatinine-corrected ICC, 0.52; 95% CI, 0.37 to 0.87) and 4-OH-TPHP (0.56; 95% CI, 0.32 to 0.80) showed moderate-to-strong temporal reliability, while relatively weak temporal reliability was found for urinary DPHP (creatinine-corrected ICC, 0.37; 95% CI, 0.12 to 0.62). This study confirmed specific, reliable, and frequently detected biomarkers for TPHP and EHDPP and developed new biomarker of TCrP for future epidemiological research on health effects of m-aryl-OPFRs.

Different organophosphate flame retardant and metabolite concentrations in urine from male and female university students in Beijing and an assessment of exposure via indoor dust.

Organophosphate flame retardants (OPFRs) have been found in human samples and associated with adverse health effects. In the present study, OPFR and dialkyl and diaryl phosphate (DAP) concentrations in human urine were determined and differences in the concentrations in urine from males and females were investigated. Urine samples from 22 male and 26 female university students, paired dust samples from the dormitories (13 each for males and females), and 10 dust samples from university teaching buildings were analyzed. The tri-o-cresyl phosphate (TOCP), tri-p-cresyl phosphate (TPCP), and tris(2-chloroisopropyl)phosphate (TCIPP) concentrations were significantly higher (p = 0.049, 0.023, and 0.027, respectively) in urine from the female students than in urine from the male students. Similar differences were found between males and females in terms of OPFR exposure and OPFR concentrations in urine for three-fourths of the OPFRs. Questionnaire answers and calculations indicated that disparities in OPFR concentrations in urine were mainly caused by females spending much more time than males in dormitories. Organophosphate flame retardants may pose degrees of health risk similar to those of polybrominated diphenyl ethers (PBDEs), and this must be considered when making decisions about controlling flame retardants. We are not aware of any previous studies that simultaneously monitor OPFRs and DAPs in human urine in China. Environ Toxicol Chem 2019;38:760-768. © 2019 SETAC.

Metabolites of organophosphate esters in urine from the United States: Concentrations, temporal variability, and exposure assessment.

Organophosphate esters (OPEs) are widely used as flame retardants and plasticizers in consumer products, which contributes to widespread exposure of humans. OPE diester metabolites in urine have been used as biomarkers of human exposure to these chemicals. Little is known, however, about occurrence and temporal variability in urinary concentrations of OPE metabolites in humans. In this study, 11 OPE metabolites were measured in 213 urine samples collected from 19 volunteers from Albany, New York, United States, at 3-day intervals for five weeks to investigate temporal variability in urinary concentrations. Diphenyl phosphate (DPHP) and bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) were the major OPE metabolites, detected in all urine samples at specific gravity (SG)-adjusted concentrations (geometric mean, GM) of 1060 and 414 pg/mL and creatinine (Cr)-adjusted concentration (GM) of 404 and 156 ng/g, respectively. Inter-day variability in urinary OPE metabolite concentrations in 19 individuals was evaluated by intraclass correlation coefficients (ICCs). The inter-day variability in Cr-adjusted OPE metabolite concentrations (ICC: 0.31-0.67) was lower than those of SG-adjusted (ICC: 0.19-0.71) and unadjusted urinary concentrations (ICC: 0.24-0.74). BDCIPP (ICC: 0.68) and bis(2-chloroethyl) phosphate (BCEP) (ICC: 0.67) concentrations showed a moderate-to-high reliability over the sampling period, whereas the other nine OPE metabolites exhibited a moderate reliability (ICC: 0.31-0.55). Urine samples were further stratified by gender, age, ethnicity, and body mass index (BMI). The concentrations of BDCIPP and DPHP were significantly lower in males with normal BMI (BMI: 18.5-25 kg/m2) than in females and other BMI categories (p < 0.01). Relatively high ICCs, indicating low inter-day variability, were observed for males (ICC: 0.35-0.71) of 30-40 years of age (ICC: 0.34-0.87) with normal BMI (ICC: 0.28-0.64). The daily exposure doses to OPEs were estimated from urinary concentrations of corresponding OPE metabolites. The estimated doses of triphenyl phosphate (TPHP) and triethyl phosphate (TEP), based on median urinary concentrations of their metabolites, were 19.4 and 24.0 ng/kg bw/day, and the exposure dose to ∑OPEs was estimated at 65.3 ng/kg bw/day. Overall, our results indicate a high ICC for Cr-adjusted urinary concentrations of 11 OPE metabolites in urine.

Flame retardant exposure assessment: findings from a behavioral intervention study.

BACKGROUND: Polybrominated diphenyl ethers (PBDEs) have been largely replaced by organophosphate flame retardants (OPFRs) and alternative brominated flame retardants (Alt-BFRs) to meet flammability requirements. Humans are ubiquitously exposed to some variety of flame retardants through contact with consumer products directly or through household dust. OBJECTIVES: To evaluate the effectiveness of house cleaning and hand washing practices to reduce exposure to flame retardants, we measured concentrations in dermal hand wipes and urinary metabolites before and after assignment to two consecutive interventions. METHODS: We selected 32 mother and child dyads from an existing cohort. This analysis focuses on mothers. Participants provided baseline measurements (urine, hand wipes, and questionnaires) and were then assigned for 1 week to either a house cleaning (including instruction on proper technique and cleaning supplies) or hand washing (including instruction on proper technique and soaps) intervention arm. For the second week, participants were assigned to the second intervention in addition to their initial assignment, thus all subjects both washed their hands and cleaned according to the intervention guidelines during week 2. We collected measurements at the end of weeks 1 and 2. RESULTS: We found reductions in urinary analytes after week 1 of house cleaning (BCIPHIPP and ip-DPHP), week 1 of hand washing (BCIPP, BCIPHIPP, and tbutyl-DPHP), and week 2 of combined interventions (BCIPHIPP and tbutyl-DPHP), compare to baseline. We found no significant decline in hand wipes in the entire sample but did find reductions after week 1 of house cleaning (BDE 209), week 1 of hand washing (TCEP), and week 2 of combined interventions (TDCIPP and BDE 209) in women with exposure above the median at baseline (verified through simulations). CONCLUSIONS: Exposure to individual flame retardants was reduced by about half, in some cases, by 1 week of increased hand washing, house cleaning to reduce dust, or combined activities.

Simultaneous assessment of phenolic metabolites in human urine for a specific biomonitoring of exposure to organophosphate and carbamate pesticides.

Organophosphate pesticides (OPP) and carbamates are still counted among the most prominent agents used for crops protection. Up to date the determination of dialkylphosphates and their thio derivatives in urine is established for the OPP biomonitoring. However, this approach does not provide information on the exposure to specific OPP agents. A lot of OPP as well as some carbamates also provide specific urinary biomarkers indeed. Analytical methods for the determination of phenolic metabolites of OPP and carbamates have already been established by different working groups. However, these approaches only acquire one or few analytes. Therefore, we developed an analytical procedure which enables the simultaneous assessment of a wide spectrum of phenolic metabolites of OPP, carbamates and other pesticides in human urine using GC-MS/MS. The method includes enzymatic hydrolysis, solid phase extraction, derivatization, and subsequent GC-MS/MS analysis. The method showed detection limits between 0.1 and 0.4 µg/l. Variation coefficients ranged from 1 to 9 % for precision in series and 1 % to 13 % for inter-day precision. Furthermore, recovery rates between 87 and 117 % were determined. Compared with other published analytical procedures, the present method enables the simultaneous monitoring of a much broader spectrum of pesticides and biocides whose structures contain aryl moieties with competitive or improved analytical reliability. Furthermore, the suitability of the developed procedure was verified through the successful application to urine samples of pesticide exposed humans.

Correlation of pesticide exposure from dietary intake and bio-monitoring: The different sex and socio-economic study of children.

Exposure to organophosphorus pesticides was assessed though bio-monitoring of urinary dialkyl phosphate metabolites to characterize children's exposure to pesticides. No reports have been found which evaluate exposure of pesticides among adolescents of different sexes. The primary objective was to develop a coupled exposure-dose modeling approach that can be used to determine the metabolite concentrations. Related objective was to determine any significant changes of pesticide exposure among the adolescents of different sexes. The primary objective was to develop a coupled exposure-dose modeling approach to determine the metabolites concentrations to keep children's urine metabolites levels below specified values considering exposures from water, and the food related objective was to determine any significant changes of pesticide exposure among the adolescents of different sexes. We recruited a sample of 377 children (188 boys, 189 girls) ages 6-10 and 11-15 years from Hyderabad, India for urine collection. Results showed that the mean concentrations of dialkyl phosphate metabolites in first morning first urine samples (3.05 µmol L-1) were strongly correlated with concentrations of the same-day 24-h samples (1.7 µmol L-1) ( r = 0.997, model R2 ≈ 0.994, p < 0.00) with 99.4% accuracy. Irrespective of similar amounts of conventional food consumption, girls showed 87.5% of detection frequency of DAP metabolites which was higher than the 74% detection frequency of DAP metabolites among boys. The female group showed (87%) higher pesticide metabolite levels than boys. This report may help to focus on new studies of the connection between adolescents of different sex and organophosphorus metabolite exposure and to develop an exposure database to facilitate health risk assessment in our day-to-day environment.

Determinants of organophosphate pesticide exposure in pregnant women: A population-based cohort study in the Netherlands.

BACKGROUND: In the Netherlands organophosphate (OP) pesticides are frequently used for pest control in agricultural settings. Despite concerns about the potential health impacts of low-level OP pesticides exposure, particularly in vulnerable populations, the primary sources of exposure remain unclear. The present study was designed to investigate the levels of DAP metabolites concentrations across pregnancy and to examine various determinants of DAP metabolite concentrations among an urban population of women in the Netherlands. METHOD: Urinary concentrations of six dialkyl phosphate (DAP) metabolites, the main urinary metabolites of OP pesticides, were determined at <18, 18-25, and >25 weeks of pregnancy in 784 pregnant women participating in the Generation R Study (between 2004 and 2006), a large population-based birth cohort in Rotterdam, the Netherlands. Questionnaires administered prenatally assessed demographic and lifestyle characteristics and maternal diet. Linear mixed models, with adjustment for relevant covariates, were used to estimate associations between the potential exposure determinants and DAP metabolite concentrations expressed as molar concentrations divided by creatinine levels. RESULTS: The median DAP metabolite concentration was 311 nmol/g creatinine for the first trimester, 317 nmol/g creatinine for the second trimester, and 310 nmol/g creatinine for the third trimester. Higher maternal age, married/living with a partner, underweight or normal weight (BMI of <18.5 and 18.5-<25), high education, high income, and non-smoking were associated with higher DAP metabolite concentrations, and DAP metabolite concentrations tended to be higher during the summer. Furthermore, fruit intake was associated with increased DAP metabolite concentrations. Each 100 g/d difference in fruit consumption was associated with a 7% higher total DAP metabolite concentration across pregnancy. Other food groups were not associated with higher DAP metabolite concentrations. CONCLUSIONS: The DAP metabolite concentrations measured in the urine of pregnant women in the Netherlands were higher than those in most other studies previously conducted. Fruit intake was the main dietary source of exposure to OP pesticides in young urban women in the Netherlands. The extent to which DAP metabolite concentrations reflect exposure to the active parent pesticide rather than to less toxic metabolites remains unclear. Further research will be undertaken to investigate the possible effects of this relatively high level OP pesticides exposure on offspring health.

Farmworker and nonfarmworker Latino immigrant men in North Carolina have high levels of specific pesticide urinary metabolites.

This article compares detections and concentrations of specific organophosphate (OP), bis-dithiocarbamate, and pyrethroid pesticide urinary metabolites among Latino male farmworkers and nonfarmworkers in North Carolina. Data are from interviews and urine samples collected in 2012 and 2013. Farmworkers and nonfarmworkers frequently had detections for OP and pyrethroid pesticide urinary metabolites. Detection of bis-dithiocarbamate urinary metabolites was less frequent, but substantial among the nonfarmworkers. The concentrations of organophosphate, bis-dithiocarbamate, and pyrethroid pesticide urinary metabolites were high for farmworkers and nonfarmworkers compared to National Health and Nutrition Examination Survey results. Pesticide urinary metabolite detection was not associated with occupation in nonfarmworkers. Research for reducing pesticide exposure among farmworkers remains important; research is also needed to determine pesticide exposure pathways among Latino nonfarmworkers.

Variability and predictors of urinary concentrations of organophosphate flame retardant metabolites among pregnant women in Rhode Island.

BACKGROUND: Organophospate flame retardants (PFRs) are chemicals of emerging concern due to restrictions on polybrominated diphenyl ether flame retardant formulations. We describe the occurrence, variability, and predictors of urinary metabolites of PFRs among pregnant women. METHODS: In 2014-2015, 59 women from Providence, RI provided up to 3 spot urine samples during pregnancy (~12, 28, and 35 weeks' gestation). We created a pooled urine sample per woman and measured nine relevant metabolites in individual and pooled samples. We used linear mixed models to calculate intraclass correlation coefficients (ICCs) across the 3 measurements and to assess sociodemographic and dietary predictors of PFRs. RESULTS: The median (IQR) of bis-2-chloroethyl phosphate (BCEP), bis(1,3-dichloro-2-propyl) phosphate (BDCPP), and diphenyl phosphate (DPhP), the metabolites most frequently detected, from pooled samples were: 0.31 µg/L (0.17-0.54), 1.18 µg/L (0.64-2.19), 0.93 µg/L (0.72-1.97), respectively. We observed fair to good reproducibility for BCEP (ICC = 0.50), BDCPP (ICC = 0.60), and DPhP (ICC = 0.43), and excellent agreement between the urinary flame retardant metabolite concentrations averaged across pregnancy versus pooled urine sample concentrations for BCEP (ICC = 0.95), BDCPP (ICC = 0.89), and DPhP (ICC = 0.93). Adjusting for pertinent sociodemographic factors and gestational week of urine collection, each 1 kg increase in pre-pregnancy weight was associated with greater BCEP (1.1%; 95% CI: 0.1, 2.1), BDCPP (1.5%; 95% CI: 0.3, 2.7), and DPhP (0.5%; 95% CI: 0.0, 1.1). Dietary factors were generally not associated with urinary flame retardant metabolites. CONCLUSIONS: Urinary concentrations of BCEP, BDCPP, and DPhP were frequently detected among women in this pilot study and had fair reproducibility across pregnancy. Body size may be an important predictor of urinary flame retardant metabolite concentrations.

Occupational predictors of urinary dialkyl phosphate concentrations in Mexican flower growers.

Background Flower growers have high potential for exposures to pesticides. Occupational factors, such as tasks performed, the production method (organic or conventional), the use of personal protective equipment (PPE), and workplace characteristics influence the intensity of pesticide exposure. Objective To evaluate occupational characteristics affecting urinary concentration of dialkylphosphate (DAP) metabolites of organophosphate pesticides among a group of Mexican floricultural workers. Methods A questionnaire was administered to 117 workers who also provided a first morning urine sample. According to tasks performed and the production methods, pesticide contact was defined as low, medium, or high. PPE use was categorized as acceptable, fairly acceptable, and unacceptable. Urinary concentration of DAP metabolites were determined using gas-liquid chromatography. Association between occupational characteristics and DAP urinary concentrations was assessed by means of linear regression models. Results After adjusting for potential confounders, the workers in the medium and high contact categories had significantly higher DAP concentrations than those in the low contact category (ß: 0.3, CI 95%: 0.1-0.5). Greenhouse workers had greater DAP concentrations than outdoors workers (ß: 0.3, CI 95%: 0.1-0.5). Compared with non-acceptable use of PPE, acceptable use of PPE was associated with lower DAP concentrations (ß: -0.4, CI 95% -0.6 to -0.1). Conclusion Improved safety training is needed for correct PPE usage, especially among flower growers who use conventional pest control methods and who work in a greenhouse environment.

Population-based comparison of biomarker concentrations for chemicals of concern among Latino-American and non-Hispanic white children.

Differences in cultural and economic status may place ethnic subgroups of children at higher risk for exposure, leading to heightened health risks, and health inequities. Although Latino-Americans represent 22% of all children in the United States, few studies have explored within-group differences in their exposure to toxicants. Using socio-demographic and biomarker data from the National Health and Nutrition Examination Survey from 1999 to 2008, we characterized determinants of health and estimated geometric means of environmental contaminant biomarkers (blood concentrations of lead and mercury, serum concentrations of dichlorodiphenyldichloroethylene [p,p'-DDE] and cotinine, and urinary metabolites of organophosphate [OP] pesticides and polycyclic aromatic hydrocarbons [PAHs]) among 4,257 Mexican American (MA), 677 Other Latino-American (OL), and 3,370 Non-Hispanic White (NHW) children. MAs had the lowest levels of health insurance coverage and regular access to health care, and largest household size compared to NHWs and OLs. MAs had higher levels of p,p'-DDE, lead, and cadmium while OLs had higher estimates of mercury relative to other groups. MAs had higher urinary metabolite concentrations of 2-hydroxynaphthalene; otherwise MAs and OLs had lower concentrations of PAHs. NHWs had higher levels of cotinine and dimethylthiophosphate. For other OP metabolites, differences among groups were less clear. Lead and p,p'-DDE exposure differences likely reflect later and less regulatory control of these chemicals in Latin America. Additionally, poor quality housing with lead paint is more common in economically disadvantaged subpopulations. Dietary habits are possible sources of differential cadmium, mercury, and organophosphate exposure. Cotinine exposure differences by income and U.S.- vs. foreign-born may represent increased acculturation. These results, coupled with additional research on exposure sources may contribute to refinement of environmental health promotion programs for the fast-growing Latino-American population.

Biomonitoring exposure assessment to contemporary pesticides in a school children population of Spain.

The exposure to pesticides amongst school-aged children (6-11 years old) was assessed in this study. One hundred twenty-five volunteer children were selected from two public schools located in an agricultural and in an urban area of Valencia Region, Spain. Twenty pesticide metabolites were analyzed in children's urine as biomarkers of exposure to organophosphate (OP) insecticides, synthetic pyrethroid insecticides, and herbicides. These data were combined with a survey to evaluate the main predictors of pesticide exposure in the children's population. A total of 15 metabolites were present in the urine samples with detection frequencies (DF) ranging from 5% to 86%. The most frequently detected metabolites with DF>53%, were 3,5,6-trichloro-2-pyridinol (TCPy, metabolite of chlorpyrifos), diethyl phosphate (DEP, generic metabolite of OP insecticides), 2-isopropyl-4-methyl-6-hydroxypyrimidine (IMPY, metabolite of diazinon) and para-nitrophenol (PNP, metabolite of parathion and methyl parathion). The calculated geometric means ranged from 0.47 to 3.36 µg/g creatinine, with TCPy and IMPY showing the higher mean concentrations. Statistical significant differences were found between exposure subgroups (Mann-Whitney test, p<0.05) for TCPy, DEP, and IMPY. Children living in the agricultural area had significantly higher concentrations of DEP than those living in the urban area. In contrast, children aged 6-8 years from the urban area, showed statistically higher IMPY levels than those from agricultural area. Higher levels of TCPy were also found in children with high consumption of vegetables and higher levels of DEP in children whose parents did not have university degree studies. The multivariable regression analysis showed that age, vegetable consumption, and residential use of pesticides were predictors of exposure for TCPy, and IMPY; whereas location and vegetable consumption were factors associated with DEP concentrations. Creatinine concentrations were the most important predictors of urinary TCPy and PNP metabolites.

Pesticide risk perception and biomarkers of exposure in Florida female farmworkers.

OBJECTIVE: To compare workplace characteristics, workplace behaviors, and the health beliefs of female farmworkers of childbearing age with actual biomarkers of exposure to organophosphate pesticides and to the fungicide mancozeb. METHODS: Hispanic and Haitian farmworkers between the ages of 18 and 40 years working in nursery or fernery operations were recruited to participate in a cross-sectional survey, examining demographics, work practices, work-related hygiene, and pesticide exposure beliefs. Single-void (spot) urine samples were analyzed for organophosphate and ethylenethiourea metabolites. RESULTS: Women in nurseries worried less frequently about the effects of pesticides on their health than those in fernery operations. In summary, organophosphate and ethylenethiourea levels in nursery workers were significantly higher than levels in fernery workers and the control group. CONCLUSIONS: Results showed that perceived pesticide exposure did not correspond to actual metabolite levels within differing agricultural subpopulations.